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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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Isothermal drop calorimeter provides measurements for alpha active, pyrophoric materials

Isothermal drop calorimeter measures the heat content of intensely alpha active and pyrophoric materials in inert atmospheres. It consists of a furnace, calorimeter, and aluminum isothermal jacket contained within an inert-atmosphere glove box, which permits the use of unencapsulated materials without exposing personnel to alpha contamination.

Savage, H.↗

MSTEC: Molten Salt Thermophysical Examination Capability

Technical Description – a shielded modular hotcell with an inert argon atmosphere, housing characterization equipment for determining thermophysical and thermochemical properties of high temperature liquids not limited to but focusing on irradiated fuel salts Location – MFC, FCF, rm 35 Compatible Materials: Chloride, fluoride salts Fresh fuel salts and irradiated fuel salts Pyrophoric material - U, Pu metal Gases – H2, HCl, Cl2, HF, F2, NF3 Beryllium containing salts Many others

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Apparatus for remote handling of materials

Apparatus for remote handling of materials are described. A closed housing is provided with first and second containers and first and second reservoirs for holding materials to be mixed. The materials are transferable from the reservoirs to the first container where they are mixed. The mixed materials are then conveyed from the first container to the second container preferably by dumping the mixed materials into a funnel positioned over the second container. The second container is then moved to a second position for analysis of the mixed materials. For example, the materials may be ignited and the flame analyzed. Access, such as a sight port, is provided in the housing at the analysis position. The device provides a simple and inexpensive apparatus for safely mixing a pyrophoric material and an oxidizer which together form a thermite type mixture that burns to produce a large quantity of heat and light.

Kimball, R. B.↗

Uranium corrosion characterization by handheld laser-induced breakdown spectroscopy

In this study, a commercial-off-the-shelf handheld laser-induced breakdown spectroscopy system was modified, calibrated and tested for discrimination between uranium oxide and uranium hydride when assessing uranium corrosion products. Operating parameters, system modifications, and onboard data analysis were developed to accomplish the analytical task. This work represents the first laser-induced breakdown spectroscopy analysis of bulk uranium hydride, a pyrophoric material, within an inert glovebox. Finally, the work shown here illustrates a rapid identification technique for uranium corrosion types from pure UO 2 or U 3 O 8 to pure UH 3 .

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Advanced Mixed Waste Treatment Project Overcomes Challenges to Complete Treatment of Debris Waste - 20616

The Advanced Mixed Waste Treatment Project (AMWTP), operated by Fluor Idaho for the Department of Energy Idaho Operations Office, completed the last of its debris waste treatment in the fall of 2019. Concluding that work-scope was certainly not without its challenges. Fluor Idaho and its employees had to adapt to treating extremely challenging waste types, such as high-fissile gram materials and potentially pyrophoric and reactive wastes coming down the stretch. It also had to complete the sizing of large waste boxes from Mound Laboratories in inner-contamination enclosures designed to capture the extremely fine, 'flighty' plutonium-238 in its high-efficiency particulate air filters. Very few waste treatment facilities in the DOE Complex have completed their missions. In fact, most large-scale waste treatment facilities are still under construction with many months or years remaining before 'hot operations' begin. AMWTP is unique because it functioned as a 'one-stop shop.' Transuranic and low-level waste characterization, treatment, certification, and shipping all occurred there. AMWTP concluded the most challenging part of its mission and will continue to ship material out of the state of Idaho for the next decade. This paper will provide a background of the AMWTP mission, and the adaptations to its operating permit, equipment, or treatment processes to address challenging waste types. AMWTP will leave behind a legacy of being one of the most successful waste treatment facilities in the history of the DOE Complex. The facility was well-conceived, well-constructed, and well-executed; it was done right from start to finish. During the course of its waste treatment mission, the facility was required to adapt to changing conditions by treating extremely challenging waste types. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Elastic moduli of high-density, sintered monoliths of yttrium dihydride

Yttrium dihydride has been considered as potential nuclear reactor moderator for micro-reactors operating in the thermal energy spectrum due to their ability to retain hydrogen to high temperatures while having a relatively low impact on neutron economy. Despite these advantages, it is difficult to prepare yttrium dihydride in high-density, near net-shape monoliths for moderator applications due to volume expansion upon hydriding and the pyrophoric nature of the material. In this work, high-density monoliths of yttrium dihydride were prepared by direct hydriding and using powder metallurgical methods. Resonant ultrasound spectroscopy was used to measure the elastic moduli of the sintered monoliths, while nanoindentation was used to determine the Young’s modulus and hardness of the directly-hydrided yttrium and the sintered monoliths. Single crystal elastic constants and related properties of yttrium dihydride were also determined using density functional theory (DFT) for comparison. We report mechanical properties of materials produced by both methods were observed to be consistent with the values from literature for yttrium dihydride. Due to the novelty of producing yttrium dihydride by powder metallurgy, this result indicated that the monoliths produced by powder metallurgy were of high quality. To that end, powder metallurgy is believed to be a viable method for large-scale production of yttrium dihydride monoliths for nuclear reactor moderator applications.

36 MATERIALS SCIENCE↗

Development and evaluation of a plasma jet flameholder for scramjets

The objective of the work reported herein was to explore the use of a continuous operation plasma torch as an ignitor and flameholder for scramjet combustion. This research was motivated by the desire to eliminate the use of pyrophoric or toxic ignition and/or combustion enhancement materials in operational aircraft or shipboard systems. The total temperatures and torch powers used to ignite/flamehold Mach 2 combustion with hydrogen, ethylene, ethane, and methane were determined. The minimum ignition total temperatures for the fuels tested were hydrogen - 1065 R (lowest test temperature); ethylene - 1500 R; ethane - 2000 R; methane - 2700 R. These temperatures were obtained while operating the torch at a nominal 2 kw net power. The torch was shown to be a good ignitor and flameholder in that both hydrogen and hydrocarbon fuels could be stabilized by the torch and would 'blow off' when the torch was extinguished. The effectiveness of the torch was very sensitive to relative fuel injection location. Best combustion resulted when fuel was injected both upstream and downstream of the torch. These results indicated that an adiabatic plasma torch operating at about 2 kw could be an effective ignitor and flameholder for high-speed combustion.

Northam, G. B.↗

Elucidating the Initial Steps in α-Uranium Hydriding Using First-Principles Calculations

Hydrogen embrittlement of uranium, which arises due to the formation of a structurally weak pyrophoric hydride, poses a major safety risk in material applications. Previous experiments have shown that hydriding begins on the top or near the surface (i.e., subsurface) of α-uranium. However, the fundamental molecular-level mechanism of this process remains unknown. Here, in this work, starting from pristine α-U bulk and surfaces, we present a systematic investigation of possible mechanisms for the formation of metal hydride. Specifically, we address this problem by examining the individual steps of hydrogen embrittlement, including surface adsorption, subsurface absorption, and the interlayer diffusion of atomic hydrogen. Furthermore, by examining these processes across different facets, we highlight the importance of both (1) hydrogen monolayer coverage and (2) applied tensile strain on hydriding kinetics. Taken together, by studying previously overlooked phenomena, this study provides foundational insights into the initial steps of this overall complex process. We anticipate that this work will guide near-term future development of multiscale kinetic models for uranium hydriding and subsequently identify potential strategies to mitigate this undesired process.

36 MATERIALS SCIENCE↗

The advanced characterization, post-irradiation examination, and materials informatics for the development of ultra high-burnup annular U-10Zr metallic fuel

U-Zr metallic fuel is a promising fuel candidate for Gen Ⅳ fast spectrum reactors. Previous experimental irradiation campaigns showed that the sodium thermal bonded U-10Zr fuel design can achieve a burnup of 10% fissions per initial heavy metal atom (FIMA). Advanced metallic fuel designs are pushing the burnup limit to 20% or even 30% FIMA. To achieve the higher burnup and eliminate the pyrophoric sodium, a prototypical annular fuel has been designed, fabricated, clad with HT-9 in the Materials and Fuels Complex, and irradiated in the Advanced Test Reactors of Idaho National Laboratory (INL) to a peak burnup of 3.3% FIMA. During irradiation, the mechanical contact between fuel and cladding acts as a thermal bond. The irradiation lasted for 132 days in the reactor. Recently, the archived fresh and irradiated fuel samples were characterized using advanced characterization capabilities in the Irradiated Materials Characterization Laboratory (IMCL) of INL. This article summarizes the results of advanced characterization and computer vision-based materials informatics to reveal the irradiation effects on U-Zr metallic fuel. Future work will focus on further implementation of advanced characterization and statistical data mining to improve the fidelity of fuel performance modeling and support U-Zr metallic fuel qualification for fast spectrum reactors.

Yao, Tiankai↗

Electronic and Geometric Contributors to Hydrogen Binding in Uranium Oxide Grain Boundaries

Hydrogen induced corrosion of uranium, which leads to the formation of toxic and pyrophoric UH 3 , raises significant safety concerns for long-term storage of nuclear materials. Previous work suggests hydrogen diffuses through the grain boundaries (GBs) of the passivating oxide layer to initiate hydriding reactions. However, the atomistic mechanisms underlying this phenomenon and the structural factors that control its initiation are not well understood. To address this knowledge gap, here we use a high-throughput density functional theory (DFT) workflow to investigate the adsorption of H and H 2 in the defective bulk UO 2 . Specifically, we have exhaustively investigated the adsorption of H (107 sites) and H 2 (26 sites) in three different coincident site lattice (CSL) GBs: Σ3, Σ5, and Σ9. Compared to the binding energies in pristine UO 2 , we observe significantly stronger hydrogen adsorption at these GB sites. Interestingly, we find that the trends in H and H 2 adsorption vary considerably across the three GB models. In particular, while a small number of sites in Σ5 and Σ9 show exothermic adsorption of H and H 2 , respectively, no such sites are found in Σ3. These results provide fundamental atomistic insights that could guide the development of future corrosion mitigation strategies for the storage of nuclear materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Removal and Deactivation of Bond Sodium from Fast Reactor Blanket Materials

The disposition of sodium-bonded spent nuclear fuel and blanket materials in a repository is complicated by the presence of sodium metal that is used as a thermal bond between the uranium metal fuel and blanket slugs and their cladding. The concern is that the metallic sodium could react with water, producing explosive hydrogen gas, or could exhibit a pyrophoric character. Thus, experimental studies were performed to investigate and demonstrate the removal and deactivation of bond sodium from blanket material in a dry environment. Specifically, bond sodium was removed from unirradiated Fermi-1 blanket elements and an assembly via a melt-drain-evaporate process using elevated temperature and reduced pressure. The effectiveness of sodium metal removal from the blanket materials and their associated cladding was =99.9998%, based on post-test quantitative analyses. The separated sodium metal was collected and subsequently deactivated by reacting it in a molten state with a controlled addition of ammonium chloride particles atop a molten salt medium. In this process sodium chloride is formed and assimilates into the salt pool. The subsequent deactivation of the bond sodium produced a solid ingot of sodium chloride, potassium chloride, lithium chloride, and cesium chloride that was devoid of sodium metal based on post-test analyses of the salt product. Both the sodium removal and deactivation operations were conducted within a dry inert atmosphere enclosure. The results of this study substantiate a path forward for the disposition of sodium-bonded blanket materials, including 34 metric tons heavy metal in irradiated Fermi-1 blanket material currently stored at Idaho National Laboratory.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Titanium Wire Arc Additive Manufacturing Inert Enclosure and Material Handling Safety Considerations

Wire arc additive manufacturing (WAAM) via metal inert gas (MIG)/gas metal arc welding (GMAW) is a viable option for fabrication of large-scale titanium parts; however, it introduces new safety hazards associated with both the material and the additional system hardware required for the process. Localized gas shielding of the weld arc via standard GMAW torch is inadequate for titanium due to its affinity for oxygen; thereby requiring the use of an inert enclosure to protect the weld from entraining oxygen. The use of the inert enclosure presents potential safety hazards such as operator asphyxiation and brings up discussion of confined space considerations. In addition, the titanium welding process creates pyrophoric titanium soot residue around the deposit, which can undergo deflagration during part cleaning and part removal. This paper provides an overview of the titanium WAAM process along with safety considerations for the design and operation of the inert enclosure as well as functional solutions for the safe handling of the titanium soot by-product.

Walters, Alex↗

Recovery of Zr from ZrCl 4 by Electrolysis in Fused Salts and Ionic Liquids: Literature Review and Test Plan

This report reviewed the current status on the research and development of Zr electrodeposition in high temperature molten salts and room temperature ionic liquids from ZrCl 4 , which is the product of the chlorination process developed for recycling the Zr claddings of the spent nuclear fuels. Due to the pyrophoricity issue, the Zr metal product from the electrodeposition process is desired to be of coarse, dense crystalline or plates (instead of powder or loose, fine crystals) that are not to be easily oxidized. The findings based on the literature review are included in the report.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Novel syntheses of carbazole-3,6-dicarboxylate ligands and their utilization for porous coordination cages

The molecular nature, and thus potential solubility, of coordination cages endows them with a number of advantages as compared to metal–organic frameworks and other extended network solids. However, their lack of three-dimensional connectivity typically limits their thermal stability as inter-cage interactions in these materials are relatively weak. This is particularly the case for carbazole-based coordination cages. Here, we report the design and synthesis of a benzyl-functionalized octahedral coordination cage that displays moderate surface area and increased thermal stability as compared to its unfunctionalized counterpart. Structural analysis suggests the increased thermal stability is a result of aryl–aryl interactions between ligand groups on adjacent cages. We have further adapted the ligand synthesis strategy to afford a novel, high-yielding preparatory route for the isolation of carbazole-3,6-dicarboxylic acid that does not rely on pyrophoric reagents or transition metal catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stability of gas atomized reactive powders through multiple step in-situ passivation

A method for gas atomization of oxygen-reactive reactive metals and alloys wherein the atomized particles are exposed as they solidify and cool in a very short time to multiple gaseous reactive agents for the in-situ formation of a protective reaction film on the atomized particles. The present invention is especially useful for making highly pyrophoric reactive metal or alloy atomized powders, such as atomized magnesium and magnesium alloy powders. The gaseous reactive species (agents) are introduced into the atomization spray chamber at locations downstream of a gas atomizing nozzle as determined by the desired powder or particle temperature for the reactions and the desired thickness of the reaction film.

36 MATERIALS SCIENCE↗

Potential safety impacts associated with production of gaseous PuF 6 due to reactions between 3013-compliant PuO 2 with Novec TM 1230 at temperature

A part of the NNSA/SRNS Surplus Plutonium Disposition (SPD) project is a planned expansion of an existing facility with capabilities to handle, process, package, and characterize large amounts of plutonium oxide materials for permanent disposition at WIPP. The facility design for this future processing capability will include glovebox operations, HEPA filters, and exhaust/ventilation systems. An NNSA review of the facility support systems included comments on the potential residual reactivity of previously-stabilized PuO 2 , and on the possibility of chemical interactions between stabilized PuO 2 and a new fire suppressant (Novec TM 1230), a replacement for chlorinated/brominated compounds such as HALON TM , to be employed in the event of a room/glovebox fire where PuO 2 will be processed.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗